Pretreatment of transparent conductive oxide (TCO) thin films for improved electrical contact

ABSTRACT

Certain embodiments relate to optical devices and methods of fabricating optical devices that pre-treat a sub-layer to enable selective removal of the pre-treated sub-layer and overlying layers. Other embodiments pertain to methods of fabricating an optical device that apply a sacrificial material layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

An Application Data Sheet is filed concurrently with this specificationas part of the present application. Each application that the presentapplication claims benefit of or priority to as identified in theconcurrently filed Application Data Sheet is incorporated by referenceherein in its entirety and for all purposes.

FIELD

Embodiments described herein generally relate to optical devices such aselectrochromic devices, and methods of fabricating optical devices.

BACKGROUND

Various optically switchable devices are available for controllingtinting, reflectivity, etc. of window panes. Electrochromic devices areone example of optically switchable devices generally. Electrochromismis a phenomenon in which a material exhibits a reversibleelectrochemically-mediated change in an optical property when placed ina different electronic state, typically by being subjected to a voltagechange. The optical property being manipulated is typically one or moreof color, transmittance, absorbance, and reflectance. One well knownelectrochromic material is tungsten oxide (WO3). Tungsten oxide is acathodic electrochromic material in which a coloration transition,transparent to blue, occurs by electrochemical reduction.

Electrochromic materials may be incorporated into, for example, windowsfor home, commercial, and other uses. The color, transmittance,absorbance, and/or reflectance of such windows may be changed byinducing a change in the electrochromic material, that is,electrochromic windows are windows that can be darkened or lightenedelectronically. A small voltage applied to an electrochromic device ofthe window will cause it to darken; reversing the voltage causes it tolighten. This capability allows for control of the amount of light thatpasses through the window, and presents an enormous opportunity forelectrochromic windows to be used not only for aesthetic purposes butalso for energy-savings.

With energy conservation being of foremost concern in modern energypolicy, it is expected that growth of the electrochromic window industrywill be robust in the coming years. An important aspect ofelectrochromic window fabrication is coating of thin films on glass toproduce an electrochromic device stack, and patterning the device stackto make it functional. Part of the patterning process includes removingportions of the device stack to reveal underlying transparent conductiveoxide (TCO) in order to fabricate electrical connections, e.g. bus bars,onto the exposed lower TCO and the upper TCO, in order to deliverelectricity to them and thus impart a potential across theelectrochromic device stack to drive its coloring function. Selectivelyremoving these materials to reveal the underlying TCO may beproblematic, e.g., depending upon the materials that make up theelectrochromic device.

SUMMARY

Embodiments described herein generally relate to optical devices such aselectrochromic devices, and methods of fabricating optical devices.

Certain embodiments pertain to a method of fabricating an opticaldevice, where the method comprises, in the following order: (a) exposinga sub-layer of the optical device to an energy source, (b) depositingone or more material layers of the optical device on the sub-layer, and(c) ablating the one or more material layers and the sub-layer with alaser to expose an underlying layer.

Certain embodiments pertain to a method of fabricating an opticaldevice, where the method comprises: i) applying a sacrificial materiallayer to a portion of the area of one or more sub-layers of the opticaldevice, ii) depositing one or more material layers of the optical deviceon the sacrificial material layer and the one or more sub-layers, andiii) applying a laser to the portion to ablate the optical device atleast down to the sacrificial material layer.

Regarding the area of the sacrificial layer in iii), the sacrificialmaterial layer may be completely removed from the portion of the area ofthe one or more sub-layers or some of the area of the sacrificial layermay remain in the area to which it was applied. Regarding depthpenetration into the sacrificial layer, in certain embodiments it isdesirable to remove the sacrificial layer completely so that anysub-layers are cleanly exposed, e.g. an underlying transparentconducting layer may be exposed for application of a bus bar. In otherembodiments, the sacrificial layer may remain after iii) to be removedin subsequent processing steps.

Certain embodiments pertain to an optically switchable device comprisinga substantially transparent substrate, a lower conductor layer disposedover the substantially transparent substrate, and a bus bar on the lowerconductor layer over a portion of the area of a substrate, wherein theremainder of the area has one or more material layers including asacrificial material layer on a sub-layer on top of the bottom conductorlayer.

These and other embodiments are described in more detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a schematic drawing of en electrochromic device disposedover a substrate in an electrochromic window construction, according toembodiments.

FIGS. 2A-2B are cross section schematic drawings depicting two sideviews of an electrochromic device disposed over a substrate, accordingto embodiments.

FIG. 2C is a schematic top view of the electrochromic device describedin relation to FIGS. 2A and 2B.

FIG. 3 is a flowchart of a process flow describing aspects of methods offabricating an optical device (e.g., electrochromic device), accordingto embodiments.

FIGS. 4 and 5 are graphs showing experimental results comparing laserablation depth vs. fluence, to ablate down to an un-treated sub-layer ofan electrochromic device, using high pattern overlap and high spotoverlap laser ablation, respectively.

FIG. 6 is a graph showing experimental results of laser ablation down toa pre-treated buffer layer in an electrochromic device, according toembodiments.

FIG. 7 is a flowchart of a process flow describing aspects of methods offabricating an optical device (e.g., electrochromic device), accordingto embodiments.

DETAILED DESCRIPTION

Embodiments described herein generally relate to optical devices andmethods of fabricating optical devices. Optical devices includeoptically switchable devices, for example, electrochromic devices.Certain embodiments pertain to methods that pre-treat a sub-layer of anoptical device during deposition of its material layers in order tochange characteristics of that sub-layer to enable subsequent selectiveremoval of the pre-treated sub-layer and overlying layers. Otherembodiments pertain to methods of fabricating an optical device thatapply a sacrificial layer during deposition of the layers of the opticaldevice, and then ablate at least down to that sacrificial layer. Thesemethods can be used to selectively remove thin films to revealunderlying transparent conductor layers, for example.

More specifically, pre-treatment embodiments relate to methods offabricating an optical device that include pre-treating a sub-layer(e.g., one or more thin films) of the optical device to enable selectiveremoval of the pre-treated sub-layer, and any additional materiallayer(s) deposited thereon. During fabrication of an optical device, forexample, there may be one or more material layers that need to beremoved to reveal an underlying layer. Pre-treatment operationsdescribed herein can locally alter the properties and morphology of thesub-layer to enable selective removal of the pre-treated area. Forexample, certain pre-treatment operations locally expose at least aportion of the sub-layer to a laser source for heat treatment or alocalized plasma treatment of the surface. Some pre-treatment operationsincrease the absorptive properties of the sub-layer and/or decrease theabsorptive properties of the underlying layer(s). Once pre-treated, thesub-layer may more readily absorb laser energy relative to theunderlying layer. Pre-treatment enables selective removal of thepre-treated sub-layer and any material that may be deposited on thatpre-treated sub-layer to uncover the underlying layer.

Certain material layers used in fabricating optical devices, e.g.electrochromic devices, comprise thin films that are largely transparent(i.e. with low absorptive properties) before pre-treatment and do notabsorb laser energy efficiently. This makes these untreated materiallayers difficult to remove, for example, by laser ablation. In somecases, attempts to remove these untreated layers using laser ablationcould undesirably remove a portion of the underlying layer as well. Evenif the untreated material layers themselves are not difficult to remove,the combination of these layers and any additional material depositedthereon may be difficult to remove via laser ablation. In certainembodiments, the relative absorption properties of the pre-treatedlayer, any layers deposited over the pre-treated layer, and anunderlying layer may be exploited in order to achieve selective removalwith laser ablation. That is, pre-treating the sub-layer can increasethe absorption properties of the sub-layer and/or decrease theabsorption properties of the underlying layer. During subsequent laserablation, the pre-treated layer may more readily absorb laser energythan the underlying layer, which allows for selective removal (orsubstantially removal) of the pre-treated sub-layer along with anymaterial layers disposed thereon.

In certain embodiments, a method comprises (a) exposing a sub-layer ofan optical device to an energy source, (b) depositing one or morematerial layers of the optical device on the sub-layer, and (c) ablatingthe sub-layer and the one or more material layers on the sub-layer usinga laser, which exposes the underlying layer. In one instance, (a) isperformed only to a portion of the entire accessible area of thesub-layer and (c) is performed to the corresponding portion on the toplayer (i.e. the portion as perpendicular projected to the top layer ofthe one or more layers deposited on the sub-layer). This pre-treatedportion will determine the portion that is selectively ablated later.The energy source used to expose (pre-treat) the sub-layer may be thesame laser as used in (c), may be another laser, or may be plasma. Incertain embodiments, the optical device may be an electrochromic device.In one embodiment where the optical devices is an electrochromic device,the method further comprises fabricating a bus bar on a lower conductorlayer that is the underlying layer exposed in (c). These methodsdescribed herein can be integrated into other methods of fabricatingoptical devices. For example, these methods may incorporate one or moresteps of the methods of fabricating electrochromic devices described inPCT International Application No. PCT/US2012/068817, titled “THIN-FILMDEVICES AND FABRICATION,” and filed on Dec. 10, 2012, and U.S. patentapplication Ser. No. 13/456,056, titled “ELECTROCHROMIC WINDOWFABRICATION METHODS,” filed on Apr. 25, 2012, both of which are herebyincorporated by references in their entirety.

Although the methods of fabrication described herein are useful for anyoptical devices, for simplicity they are described in certainembodiments herein in terms of electrochromic (EC) devices. Duringfabrication of an electrochromic device on a substrate, for example,material from one or more layers may need to be removed to uncover aportion of an underlying layer for placement of structures in contactwith the underlying layer. For example, in a bus bar pad exposeoperation, material layer(s) over an underlying conductor layer areremoved to allow for application of a bus bar in electrical contact withthe underlying conductor layer. As another example, in a laser edgedeletion (LED) operation, material layers over the substrate are removedto allow for placement of a spacer and the primary seal in contact withthe substrate, where the spacer is between two electrochromic windows inan insulated glass unit (IGU). Some examples of constructions of ECdevices that could be fabricated using methods described herein areshown in FIG. 1 and FIGS. 2A and 2B. Other examples can be found in PCTInternational Application No. PCT/US2012/068817, titled “THIN-FILMDEVICES AND FABRICATION,” and filed on Dec. 10, 2012, and U.S. patentapplication Ser. No. 13/456,056, titled “ELECTROCHROMIC WINDOWFABRICATION METHODS,” filed on Apr. 25, 2012.

FIG. 1 depicts a cross-sectional view of a construction 100 including anelectrochromic (EC) device fabricated on a substantially transparentsubstrate 130 (e.g., glass substrate), according to embodiments. The ECdevice comprises a buffer layer 118 (e.g., TiO₂ layer) disposed over alower transparent conductive (TCO) layer 120 (e.g., fluorinated tinoxide layer). As depicted, the buffer layer 118 has the thickness,t_(buffer). In some cases, the thickness of the buffer layer,t_(buffer), is between about 10 and about 50 nm thick. The illustratedEC device further comprises an electrochromic stack including anelectrochromic (EC) layer 116 (e.g., WO₃ layer), an ion conductor (IC)layer 114 (e.g. an appropriate lithium ion conducting material such aslithium tungstate), and a counter electrode (CE) layer 112 (e.g., anamorphous NiWO layer). As depicted, the lower TCO 120 has a thickness,t_(TCO2) (e.g., about 350 nm). Although not shown, the thickness of theupper TCO 110 is t_(TCO2) (e.g., about 350 nm). The IC layer 114 shownin FIG. 1 may be a separately deposited IC layer or may be aninterfacial region created between the contacting and separatelydeposited EC layer 116 and the CE layer 112. The EC device furthercomprises an upper TCO 110 (e.g., indium tin oxide layer) disposed overthe electrochromic stack. Although the depicted EC device was fabricatedwith the material layers and relative thicknesses shown, otherthicknesses and stacking orders can be used in other embodiments. Also,it should be noted that in the example shown, the sacrificial layer isreferred to as a “buffer” layer, though any material layer with theappropriate characteristics may be pretreated, overcoated with one ormore material layers, and then selectively removed in the pretreatedarea.

The methods of fabricating optical devices described herein can be usedwith electrochromic devices such as the electrochromic device shown inFIG. 1 . For example, the methods can be used to pre-treat a bufferlayer, such as the buffer layer 118 in FIG. 1 , before depositing anelectrochromic stack. The material layers of the electrochromic stackand/or upper TCO can be laser ablated to remove the material layers downto and including the pre-treated buffer layer in order to uncover theunderlying lower TCO. This may be done in preparation for applying a busbar to the lower TCO, for example. With reference to the material layerthicknesses depicted in FIG. 1 , material with a thickness of remove(e.g., about 1200 nm) would need to be removed to cleanly expose thelower TCO 120 via laser ablation for application of the bus bar.Although the sub-layer (e.g., buffer layer 118 shown in FIG. 1 ) isshown cleanly removed after laser ablation in certain illustratedexamples, in other cases, only a substantial portion of the sub-layer isremoved.

FIGS. 2A and 2B are schematic illustrations of a construction, 200,comprising an EC device fabricated on a substantially transparentsubstrate (e.g., glass substrate). FIG. 2C is a top view schematicdrawing of the construction in FIGS. 2A and 2B. FIG. 2A depictscross-section X-X′, and FIG. 2B depicts view Y-Y′, as indicated in FIG.2C. The construction 200 shown in FIGS. 2A-2C is similar to theconstruction 100 shown in FIG. 1 . The construction 200 includes anelectrochromic (EC) device fabricated on the substrate. The EC devicecomprises a diffusion barrier disposed over a lower TCO and a bufferlayer disposed over the lower TCO. The EC device further comprises anelectrochromic stack disposed over the buffer layer. The EC stackincludes an EC layer, an IC layer, and a CE layer. The EC device furthercomprises an upper TCO over the EC stack. The IC layer may be aseparately deposited IC layer or may be an interfacial region createdbetween the contacting and separately deposited EC and EC layers. A busbar 1 230 is disposed on the upper TCO of the electrochromic device anda bus bar 2 232 is disposed on the lower TCO of the electrochromicdevice. The pair of bus bars, bus bar 1 230 and bus bar 2 232 areconfigured to be electrically connected to the corresponding TCOs inorder to apply a voltage/current across the EC stack.

In the construction illustrated in FIGS. 2A-2C, edge deletion areas,240, about the perimeter, can be formed using laser ablation, forexample, in an edge deletion operation to remove the material layersabove the substrate to leave clean edges about the perimeter of the ECdevice. In one case, the edge delete width about the perimeter isbetween about 1 mm and about 20 mm wide. In another case, the edgedelete width about the perimeter is between about 5 mm and about 15 mmwide. In yet another case, the edge delete width about the perimeter isbetween about 8 mm and about 10 mm wide. In this particularconstruction, there are no laser isolation scribes used to isolate theactive region from any inactive regions of the device stack, that is,there are no inactive device regions in the final construct by virtue ofnot having to use laser isolation scribes. Such laser patterning isdescribed in U.S. patent application Ser. No. 14/362,862 titled“THIN-DEVICES AND FABRICATION,” and filed on Jun. 4, 2014, which ishereby incorporated by reference in its entirety.

The illustrated example also depicts a bus pad expose (BPE) 260 in FIG.2C. The BPE 260 is a portion of the lower TCO that is exposed so thatthe bus bar 2 232 can be formed thereon and with electrical contact tothe lower TCO. The portion of the layers of the EC device down to thelower TCO can be removed in a BPE operation to create a landing for thebus bar 2 232. Formation of the edge delete areas 240 and BPE 260 can beperformed in any order. In one embodiment, the edge deletion operationis performed before the BPE operation.

As mentioned above, a BPE (e.g., BPE 260 in FIG. 2C) can refer to aportion of the layers of an EC device that is removed down to the lowerelectrode (e.g. lower TCO) to create a surface for a bus bar to beapplied and make electrical contact with the electrode. The bus barapplied can be a soldered bus bar, an ink bus bar, and the like. A BPEtypically has a rectangular area, but this is not necessary; the BPE maybe any geometrical shape or a random shape. For example, depending uponthe need, a BPE may be circular, triangular, oval, trapezoidal, andother polygonal shapes. The shape may be dependent on the configurationof the EC device, the substrate bearing the EC device (e.g. an irregularshaped window), or even, e.g., a more efficient laser ablation patternused to create it. In one embodiment, the BPE substantially spans oneside of an EC device and is wide enough to accommodate the bus bar withspace at least between the EC device stack and the bus bar. In oneembodiment, the BPE is substantially rectangular, the lengthapproximating one side of the EC device and the width is between about 5mm and about 15 mm, in another embodiment between about 5 mm and about10 mm, and in yet another embodiment between about 7 mm and about 9 mm.As mentioned, a bus bar may be between about 1 mm and about 5 mm wide,typically about 3 mm wide.

The BPE is typically, but not necessarily, made wide enough toaccommodate the bus bar's width and also leave space between the bus barand the EC device (as the bus bar is only supposed to touch the lowerelectrode). The bus bar width may exceed that of the BPE (and thus thereis bus bar material touching both lower conductor and glass), so long asthere is space between the bus bar and the EC device. In embodimentswhere the bus bar width is accommodated by the BPE, that is, the bus baris entirely atop the lower conductor, the outer edge, along the length,of the bus bar may be aligned with the outer edge of the BPE, or insetby about 1 mm to about 3 mm. Likewise, the space between the bus bar andthe EC device is between about 1 mm and about 3 mm, in anotherembodiment between about 1 mm and 2 mm, in another embodiment about 1.5mm Formation of BPE's is described in more detail below, with respect toan EC device having a lower electrode that is a TCO. This is forconvenience only, the electrode could be any suitable electrode,transparent or not.

To form a BPE, an area over the lower electrode (e.g., TCO) is clearedof material so that a bus bar can be fabricated at the BPE. In certainembodiments, this can be achieved by laser ablation of the materialabove a pre-treated buffer layer above the lower TCO. This canselectively remove the deposited material layers while leaving the lowerTCO exposed in a defined area at a defined location (i.e. at the BPE).

In certain embodiments with an electrochromic device, the relativeabsorption properties of the transparent lower electrode and thepre-treated sub-layer (e.g., buffer layer) and any layers deposited overthe pre-treated sub-layer may be exploited in order to achieve selectiveremoval during laser ablation to form the BPE. That is, pre-treating thesub-layer can increase its absorption properties. During laser ablation,the pre-treated sub-layer will absorb the energy more readily and beselectively removed (or substantially removed) along with any materiallayers disposed on top of the sub-layer to leave the lower electrode(e.g. lower TCO) substantially intact. In certain cases, the upperportion of the lower electrode layer may also be removed in order toensure good electrical contact of the bus bar with the lower electrode,that is, by removing any mixture of TCO and EC materials that might haveoccurred during deposition in that upper portion of the lower electrode.

In certain embodiments, the same electromagnetic radiation (e.g., laserradiation) used to form the BPE can be used to perform edge deletion inthe same EC device. In certain cases, the electromagnetic radiation froma laser source is delivered to the substantially transparent substrateusing either optical fiber(s) or the open beam path. In embodiments thatuse electromagnetic radiation from a laser source, laser ablation can beperformed from either substrate side or the film side depending on thechoice of the electromagnetic radiation wavelength. The laser energydensity required to ablate the material layer thickness is achieved bypassing the laser beam through a lens. The lens focuses the laser beamto the desired shape and size. In one case, the energy density isbetween about 0.5 J/cm2 and about 4 J/cm2.

I. Fabrication Methods Comprising Pre-Treating Sub-Layer of an OpticalDevice

Certain embodiments pertain to methods of fabricating an optical device,where each method comprises, in the following order: (a) exposing asub-layer of the optical device to an energy source, (b) depositing oneor more material layers of the optical device on the sub-layer, and (c)ablating the one or more material layers and the sub-layer with a laserto expose the underlying layer (e.g., a lower conductor layer). In somecases, exposing the sub-layer to the energy source can alter theabsorptive properties of the sub-layer and, in some cases, also theunderlying material layer(s). In one embodiment, (a) is performed onlyon a portion of the area of the sub-layer and (c) is performedsubstantially on the same corresponding portion of the sub-layer. Thatis, ablation energy is applied, in this embodiment, to a portion of thetop layer that is a perpendicular projection of the portion of theunderlying layer that was pre-treated in step (a). This portion maydefine the area that is selectively ablated in (c). The energy sourceused in (a) may be the laser used in (c), may be another laser, or maybe plasma. For example, plasma etching using various gas plasmas, e.g.halogens such as fluorine, chlorine and/or bromine, is well known toremove material layers in electronic device fabrication. In certaincases, the optical device may be an electrochromic device. In oneembodiment where the optical device is an electrochromic device, themethod further comprises fabricating a bus bar on the lower conductorlayer (e.g., lower TCO) that exposed in (c). These embodiments aredescribed with reference to the process flow illustrated in FIG. 3 .

In certain embodiments, the sub-layer comprises titanium dioxide (TiO₂)and, in some cases, the sub-layer may consist of TiO₂. TiO₂ has provenuseful in many electronic device applications, including optical deviceapplications, yet without any pre-treatment, its absorptioncharacteristics can make it difficult to ablate, especially after one ormore material layers have been deposited on top of it. In order addressthis issue, the pre-treatment methods of embodiments expose thesub-layer comprising TiO₂ to the energy source to increase theabsorptive properties of this sub-layer, which may increase absorptionof laser energy for less difficult ablation. In some cases, theunderlying layers may also receive energy from the energy source and itsproperties may change accordingly. For example, if the underlying layercomprises tin oxide (e.g., SnO₂) and receives energy, its absorptiveproperties may be decreased as a result. In some embodiments, thesub-layer being pre-treated comprises TiO₂ and the underlying layer(s)comprises tin oxide. In these cases, pre-treatment of the sub-layercomprising TiO₂ may increase the optical absorption of the TiO₂sub-layer while simultaneously increasing the optical transmission ofthe underlying tin oxide layer. These changes to the relative absorptiveproperties of the sub-layer and/or underlying layer can enable selectiveremoval of the pre-treated portion of the sub-layer and thecorresponding portion of any layer or layers deposited on thepre-treated sub-layer.

As discussed above with reference to FIG. 1 and FIGS. 2A-2B, inembodiments where the optical device is an electrochromic device, theelectrochromic device may include a WO₃ electrochromic layer and anickel-based counter electrode layer. Exemplary nickel-based counterelectrode layers include doped NiO, e.g. NiWO, NiTaO, and the like.

In embodiments where the optical device is an electrochromic device, thesub-layer may be on top of and directly adjacent to, the lower conductorlayer of the electrochromic device. In one embodiment, the lowerconductor layer includes tin oxide (e.g., SnO₂) In the low-e windowfield, some transparent conductive oxides (TCOs) such as fluorinated tinoxides are formed on glass substrates and may serve as the lowerconductor layer. Some examples of conductive layer coated glasses areTEC Glass™ by Pilkington, of Toledo, Ohio and SUNGATE™ 300 and SUNGATE™500 by PPG Industries of Pittsburgh, Pa. TEC Glass™ is a glass coatedwith a fluorinated tin oxide conductive layer.

In certain embodiments where the optical device is an electrochromicdevice, the sub-layer being exposed to an energy source in step (a) maybe a TiO₂ buffer film (i.e., a buffer film comprising that TiO₂) that isdeposited adjacent to a lower transparent conductor layer of theelectrochromic device. For example, the sub-layer in FIG. 1 is thebuffer layer 118 disposed over the lower TCO 120 of the illustratedelectrochromic device. As another example, the sub-layer in FIGS. 2A-2Cis the buffer layer disposed over the lower TCO of the illustratedelectrochromic device. In certain cases, these buffer layers may be TiO₂buffer films. In selected material removal areas, e.g., where a bus baris to be applied after the later applied electrochromic device layersare removed from a selected BPE area, the TiO₂ buffer film may besubjected to a pre-treatment by an energy source prior to depositing theremaining electrochromic layers. The pre-treatment alters thecharacteristics of the TiO₂, and enables selective removal using a lasersource of the TiO₂ buffer film and the electrochromic film stack fromthe underlying TCO in the area that was pre-treated. The pre-treatmentexposure can be via a laser source and/or a localized plasma. Forexample, plasmas including atmospheric O₂, N₂/H₂, halogens, or othergases, reactive or not, may be used (reactive plasmas may chemicallychange the TiO₂ film making more absorptive, while a nonreactive plasmamay structurally alter the TiO₂ without necessarily changing itchemically. After fabricating the electrochromic film stack, thepre-treatment area is then exposed to a laser source for ablation of theTiO₂ buffer film and electrochromic film stack thereon. Laser ablationresults in uncovering the underlying TCO, allowing for good electricalcontact with the bus bar applied to the exposed TCO.

Although some embodiments described herein include a sub-layer (e.g.,buffer layer) that is described as comprising TiO₂, the sub-layer may bemade of various materials and have various properties. In certainembodiments, the sub-layer may include, for example, a metal oxide, ametal nitride, a metal carbide, a metal oxynitride, or a metaloxycarbide. In one case, the sub-layer may comprise a metal oxideselected from the group consisting of aluminum oxide, titanium oxide,TiO₂, tantalum oxide, cerium oxide, zinc oxide, tin oxide, siliconaluminum oxide, tungsten oxide, nickel tungsten oxide, and oxidizedindium tin oxide. In one case, the sub-layer may comprise a metalnitride selected from the group consisting of titanium nitride, aluminumnitride, silicon nitride, tantalum nitride, and tungsten nitride. In onecase, the sub-layer may comprise a metal carbide selected from the groupconsisting of titanium carbide, aluminum carbide, silicon carbide,tantalum carbide, and tungsten carbide. An example of a sub-layer thatis a buffer layer in an electrochromic device is the defect-mitigatinginsulating layer described in U.S. patent application Ser. No.13/763,505, entitled “DEFECT-MITIGATION LAYERS IN ELECTROCHROMICDEVICES,” filed on Feb. 8, 2013, which is hereby incorporated byreference in its entirety.

The pre-treatment operation involves exposing at least a portion of thesub-layer of the optical device to an energy source. In certainembodiments, the energy source is a laser source. In these cases,pre-treatment involves heating the sub-layer (e.g., TiO₂ layer) veryquickly (for example, within 10-500 nanoseconds) to temperaturesexceeding 400° C. to increase the optical absorption properties of thesub-layer. In one case, the sub-layer is heated within 10-20nanoseconds. If the sub-layer comprises TiO₂ and the underlying layercomprises tin oxide (e.g, SnO₂), the pre-treatment may increase opticalabsorption of the TiO₂ layer while simultaneously increasing the opticaltransmission of the underlying tin oxide. In addition, pre-treatment ofa sub-layer comprising TiO₂ can also localize cracking of the TiO₂ atsufficient laser fluences. After deposition, laser energy is more highlyabsorbed by the pre-treated sub-layer (e.g., TiO₂ layer) as compared tothe un-treated sub-layer, so that pre-treatment increases selectivity ofthe process of removal of pre-treated sub-layer. In some cases, thelaser firing frequency during pre-treatment may be set to 10 kHz.

In other embodiments, the energy source is a plasma. Using a plasma,pre-treatment involves exposing the surface of the sub-layer (e.g., TiO₂layer) to an atmospheric-pressure plasma, resulting in cracking of thesurface and higher absorption of water into the underlying layer(s) of,for example, of a film stack. In some embodiments, the plasmapre-treatment is performed selectively on an area or areas of thesub-layer (e.g., films) that are to be removed after optical devicefabrication thereon. After deposition of subsequent electrochromic filmlayers, the morphology of the sub-layer (e.g., TiO₂ layer) results inhigher absorption of the laser energy in the pre-treated areas,resulting in increased selectivity of the process to removal ofsub-layer in the pre-treated areas.

In certain aspects, pre-treatment process includes the intentionalalteration of a TiO₂ film or other sub-layer for increased laserabsorption through alteration of material properties (extinctioncoefficient, optical absorption) and morphology (localizedcracking/discontinuity) in the TiO₂ film or other sub-layer. Duringfabrication of electrochromic devices, applying these processes beforethe remaining layers of the electrochromic film are deposited enablesgreater control and selectivity of the laser removal process after theremaining layers of the electrochromic film stack have been deposited.As discussed above, the sub-layer need not be TiO₂, but can be othermaterials whose absorption characteristics make them difficult to removeafter one or more material layers have been deposited thereon.Embodiments described herein widen the process window in which goodelectrical contact can be made between bus bar and lower TCO, henceimproving manufacturing consistency and factory yield.

FIG. 3 is a flowchart of a process flow 400 describing aspects of amethod of fabricating an optical device (e.g., electrochromic device)according to embodiments that involve pre-treating a sub-layer of theoptical device. Although these embodiments are described with referenceto electrochromic devices in some cases, these methods can be used withother optical devices.

At step, 410, a surface of a sub-layer of an optical device is exposedto energy from an energy source. The energy source applied can be from alaser source and/or localized plasma (e.g., atmospheric O₂, N₂/H₂,halogens or other gases may be used). The sub-layer is disposed over anunderlying layer(s). In some cases, the sub-layer may comprise TiO₂and/or the underlying layer may comprise SnO₂. In cases where theoptical device is an electrochromic device, the sub-layer may be abuffer layer (e.g., buffer layer 118 in FIG. 1 ) over a lower TCO or maybe a layer (e.g., diffusion layer) over the substantially transparentsubstrate. Exposing the sub-layer to the energy source may alter theproperties and/or morphology of the sub-layer and/or the underlyinglayer(s), particularly the absorptive properties as described herein.

In some cases, only a portion of the surface area of the sub-layer isexposed to the energy source in step 410. This portion can define thedesired area that will be selectively removed (e.g., ablated) in step430. An example of a portion of a sub-layer that may be exposed in step410 is the BPE 260 on the lower TCO, which is shown in FIGS. 2A-2C.Another example of portions of a sub-layer are edge delete areas 240that may be located on a layer (e.g., diffusion layer) over thesubstantially transparent substrate. In certain cases, this portion maybe about or slightly larger than the area that is desired to be removedlater. For example, by making the initially exposed area slightly largerthan the area that is ultimately removed, a perimeter of the exposedmaterial is left behind. This may be advantageous if the material is,e.g., more insulating than it would otherwise be if not exposed to theenergy. This peripheral material might then act as an insulatingmaterial between a bus bar and the device stack to ensure the bus bardoes not make direct contact with the edge of the device stack layers(overlying the TCO to which it does make electrical connection). Thisperipheral material might also act to “contain” bus bar ink prior tocuring, as it is higher in profile and may surround the area where thebus bar ink is deposited or at least serve as a dam to impede the flowof bus bar ink toward the device stack.

At step 420, one or more material layers are deposited on thepre-treated sub-layer. In embodiments where the optical device is anelectrochromic device, step 420 may comprise depositing the EC stackand/or upper TCO over the pre-treated sub-layer such as, for example, toform the EC device shown in FIG. 1 or FIGS. 2A-2C.

At step 430, the optical device is ablated with a laser source to atleast substantially remove the pre-treated sub-layer and the one or morematerial layers deposited over the pre-treated layer. The laser sourceused in this step 430 for ablation may be the same energy source used instep 410.

In some cases, only a portion of the sub-layer and overlying layer(s) isablated in step 430. For example, the ablation energy may be applied toa selected area of the optical device that is desired to be removed. Incertain aspects, this selected area may correspond to the portion of thesub-layer that was pre-treated (exposed) in step 410. An illustratedexample of area of an electrochromic device that may be selected forablation is the BPE 260 shown in FIG. 2C. In embodiments where theoptical device is an electrochromic device, step 430 may compriseremoving the buffer layer over the lower TCO and the material layers ofan electrochromic film stack and/or upper TCO over the buffer layer.This step may result in revealing the underlying conductive TCOappropriately (e.g. cleanly removing any overlying material layers) toallow for good electrical contact with a bus bar applied to the exposedlower TCO. In step 430, the pre-treated sub-layer and overlying layer(s)are substantially removed, some de minimus amount of material from theselayers may remain. This residual material may be removed in additionaloperations, for example, by mechanical means, by additional ablationoperations, etc. In other cases, the pre-treated sub-layer and overlyinglayer(s) are cleanly removed in step 430.

In certain aspects, the illustrated method shown in FIG. 3 may includeadditional processing steps used in fabricating optical devices. Incases where the optical device is an electrochromic device, for example,the method may further comprise fabricating a bus bar over theunderlying layer exposed in step 430. In this case, the underlying layeris a lower conductor (e.g., lower TCO in FIGS. 1, 2A, and 2B).Additional processing steps that can be included in the illustratedmethod can be found in PCT International Application No.PCT/US2012/068817, titled “THIN-FILM DEVICES AND FABRICATION,” and filedon Dec. 10, 2012, and U.S. patent application Ser. No. 13/456,056,titled “ELECTROCHROMIC WINDOW FABRICATION METHODS,” filed on Apr. 25,2012.

In certain aspects, methods of embodiments described herein canselectively remove thin films from an optical device to revealunderlying transparent conductor layers. These methods can be used toselectively remove material layers from an electrochromic device toreveal the lower TCO layer, for example. During fabrication ofelectrochromic devices, the lower TCO may need to be locally exposed forapplication of a bus bar to the exposed area. In these cases, the methodmay be exposing the lower TCO layer and the sub-layer being pre-treatedmay comprise one or more buffer layers (e.g., SnO₂ and TiO₂ bufferfilms) deposited over the lower TCO, for example, prior to depositingthe electrochromic film stack. The pre-treatment alters thecharacteristics of the TiO₂ and hence enables selective removal of theTiO₂ and any layers deposited on the buffer layer(s) from the underlyingTCO layer using a laser source. For example, if the lower TCO is beingexposed, the electrochromic film stack may be deposited over thepre-treated buffer layer(s), and the pre-treatment area is exposed to alaser source for ablation of the TiO₂ and electrochromic film stack. Theresults in exposure of the underlying lower TCO, which can allow forgood electrical contact with a bus bar applied to the exposed area ofthe TCO.

II. Experimental Results from Pre-Treatment of an Electrochromic Device

Experimental results in this section are based on an EC device similarto the one illustrated in FIG. 1 with the material layers andthicknesses shown. The EC device includes a buffer layer comprising TiO₂(i.e. a TiO₂ layer) on a lower TCO (of, e.g., fluorinated tin oxide).The EC stack includes an electrochromic layer (e.g., WO₃ layer) acounter electrode layer (e.g., NiWO) and an upper TCO (indium tin oxide)in the thickness shown. Experiments were performed where the materiallayers were laser ablated in an attempt to remove all the layers down toand including the TiO₂ layer in order to reveal the lower TCO for a busbar application. In this EC device, approximately 1200 nm of materialwas needed to be removed (i.e. t_(remove) was 1200 nm) in order tocleanly expose the lower TCO via laser ablation. The TiO₂ layer wasapproximately 10-50 nm thick.

Experiments were run for both without pre-treatment (control) and withpre-treatment of the TiO₂ layer prior to deposition of the layers on topof the TiO₂. FIGS. 4 and 5 show results for the control case where theTiO₂ layer is not pre-treated. FIG. 6 shows results when the TiO₂ layerhas been pre-treated prior to deposition of the layers on top of theTiO₂.

FIGS. 4 and 5 show the graphical results of the ablation depth vs.fluence (i.e., laser energy), using high pattern overlap and high spotoverlap, respectively. High overlap in this context means that asignificant amount of the laser pattern or spot was overlapped withsubsequent laser patterns or spots in order to accomplish the desiredablation depth (e.g., about 1200 nm). High spot overlap results inhigher heating and therefore less fluence is required to ablate thematerial layers to the desired 1200 nm ablation depth. Referring to theillustrated results shown in FIGS. 4 and 5 , it can be noted that a verynarrow process window results in the control experiments. Referring toFIG. 4 that uses high pattern overlap, for example, ablation depth thatis close to 1200 nm as shown by the dotted circle could only be achievedwith application of laser fluence at about 1.8 and 1.9 J/cm², that is,within a tight range of 0.1 J/cm². Referring to FIG. 5 that uses highspot overlap, an ablation depth of about 1200 nm was achieved only withapplication of laser fluence between 1.7 and 1.80 J/cm², again within atight range of only 0.1 J/cm². In FIG. 5 , the data point at fluencelevel of 1.4 J/cm2 may be high due to measurement noise.

Pre-treating the sub-layer can widen the process window of the laserfluence levels needed to ablate to the desired ablation depth. That is,the range of laser fluence levels that can be used to accomplish adesired laser ablation depth may be widened if pre-treatment is used onthe sub-layer being ablated. For example, with reference to theelectrochromic device used in the experiments in this section, bypretreating the TiO₂ buffer layer prior to depositing the remainingmaterial layers of the electrochromic device, and then laser ablating, amuch wider process window can be achieved in the removal step. This isshown in FIG. 6 . The x-axis of the graph in FIG. 6 representspre-treatment laser fluence levels applied to the TiO₂ buffer layer inthe electrochromic device. The y-axis shows the ablation depth at fourlaser ablation fluence levels: (1) 1.8 J/cm², (2) 1.9 J/cm², (3) 2.0J/cm², and (4) 2.3 J/cm². The results show the different ablation depthsachieved by these four laser ablation fluence levels (y-axis) based thefluence level used to pre-treat the sub-layer (x-axis). The dotted linesin the x-direction denote the desired target ablation depth of 1200 nm.For the laser ablation level of 2.3 J/cm², there is no dotted linebecause this fluence level resulted consistently removing not only thepre-treated buffer layer, but also a substantial portion of theunderlying TCO (thus 2.3 J/cm² was too high fluence level). As shown,pre-treatment of the sub-layer with a fluence level between about 1.0and 2.0 J/cm² allowed for removal of the desired ablation depth about(1200 nm) for not only 1.8 and 1.9 J/cm² ablation fluence levels, butalso for 2.0 J/cm² ablation fluence. Thus, the range of ablation fluencelevels for the desired ablation depth was increased (doubled) ascompared to control—a much larger process window for ablation wasachieved using pre-treatment of the sub-layer (and the pre-treatment hasa wide process window as well, between 1.0 and 2.2 J/cm² fluencelevels).

III. Fabrication Methods with a Sacrificial Material Layer

In certain embodiments, a sacrificial material layer is applied to aselected area of the one or more sub-layers of an optical device. Thematerial and thickness used in this sacrificial material layer areselected to provide desired absorptive properties) that allow forcontrol over the thermal flux once the laser ablation of the selectedarea is performed. For example, the material and thickness of thesacrificial material layer may be selected to control the thermal fluxto a bus bar pad expose of a buffer layer in order to expose a lower TCOfor bus bar application in an electrochromic device.

Thus, certain embodiments are directed to a method of fabricating anoptical device that includes applying a sacrificial material layerduring the deposition process. In certain cases, the method comprises:i) applying a sacrificial material layer (e.g., thin film) to one ormore sub-layers of the optical device; where the sacrificial materiallayer is applied only to a portion of the area of the one or moresub-layers of the optical device; ii) depositing one or more materiallayers of the optical device on the sacrificial material layer and theone or more sub-layers; and iii) applying a laser to the portion toablate the optical device at least down to the sacrificial materiallayer. The optical device can be an electrochromic device. The one ormore sub-layers may include a buffer layer such as a buffer layercomprising TiO₂. In one embodiment, the electrochromic device includes aWO₃ electrochromic layer and a nickel-based counter electrode layer. Thenickel-based counter electrode layer may include NiWO or NiTaO. Incertain embodiments, the one or more sub-layers are on top of anddirectly adjacent to, the lower conductor layer (e.g., lower TCO) of theelectrochromic device. In certain cases, the lower conductor layer maycomprise SnO₂. In certain embodiments, the lower conductor layer issubstantially intact after iii). In one embodiment, the method furtherincludes fabricating a bus bar on the lower conductor layer exposed iniii).

FIG. 7 is a flowchart of a process flow 500 describing aspects of amethod of fabricating an optical device (e.g., electrochromic device)according to embodiments that involve applying a sacrificial materiallayer to a sub-layer. Although these embodiments are described withreference to electrochromic devices in some cases, these methods can beused with other optical devices.

At step, 510, a sacrificial material layer is applied to one or moresub-layers of an optical device. The material and thickness of thesacrificial material layer may be selected to provide a desiredabsorptive property for a predefined thermal flux that will be used inlaser ablation in step 530. In certain cases, the sacrificial materiallayer is applied only to a portion of the available surface area of theone or more sub-layers of the optical device. This portion correspondsapproximately to the area that will be targeted in the laser ablation instep 530.

At step 520, one or more material layers are deposited on thesacrificial material layer. In embodiments where the optical device isan electrochromic device, step 420 may comprise depositing the EC stackand/or upper TCO over the sacrificial material layer such as, forexample, to form the EC device similar to the one shown in FIG. 1 orFIGS. 2A-2C.

At step 530, energy fluence form a laser is directed to the portion ofthe sacrificial material layer to ablate the optical device down to atleast the sacrificial material layer.

In step 530, the sacrificial material layer and overlying layer(s) areat least substantially removed. That is, in some cases, some materialfrom these layers may remain. This residual material may be removed inadditional operations, for example, by mechanical means, by additionalablation operations, etc. In other cases, the sacrificial material layerand overlying layer(s) are cleanly removed in step 530.

Although methods described herein may be described, in some cases, withreference to material layers of the electrochromic stack shown in FIG. 1or the one show in FIGS. 2A and 2B, the methods described herein canalso be used with material layers of other optical devices. For example,the methods described herein can be used with other electrochromicdevices such as those described in U.S. patent application Ser. No.14/772,055 (now U.S. Pat. No. 8,300,298) titled “ELECTROCHROMICDEVICES,” filed on Apr. 30, 2010, which is hereby incorporated byreference in its entirety.

In the description herein, numerous specific details are set forth inorder to provide a thorough understanding of the presented embodiments.The disclosed embodiments may be practiced without some or all of thesespecific details. In other instances, well-known process operations havenot been described in detail to not unnecessarily obscure the disclosedembodiments. While the disclosed embodiments will be described inconjunction with the specific embodiments, it will be understood that itis not intended to limit the disclosed embodiments.

Although the foregoing invention has been described in some detail tofacilitate understanding, the described embodiments are to be consideredillustrative and not limiting. It will be apparent to one of ordinaryskill in the art that certain changes and modifications can be practicedwithin the scope of the appended claims.

What is claimed is:
 1. An optical device comprising: a substantiallytransparent substrate; a lower conductor layer disposed on thesubstantially transparent substrate; and a bus bar disposed on the lowerconductor layer in a portion of an area of the substantially transparentsubstrate, wherein a remainder of the area of the substantiallytransparent substrate has a stack of one or more material layerscomprising a sacrificial material layer and/or a sub-layer disposed ontop of the lower conductor layer, wherein the remainder of the area ofthe substantially transparent substrate also has an upper conductorlayer disposed on top of the stack of one or more material layers. 2.The optical device of claim 1, wherein the one or more material layersof the stack comprise a WO₃ electrochromic layer and a nickel-basedcounter electrode layer.
 3. The optical device of claim 2, wherein thenickel-based counter electrode layer comprises NiWO or NiTaO.
 4. Theoptical device of claim 1, wherein the optical device is anelectrochromic device.
 5. The optical device of claim 4, wherein thesub-layer is on top of, and directly adjacent to, the lower conductorlayer of the electrochromic device.
 6. The optical device of claim 1,wherein the lower conductor layer comprises tin oxide.
 7. The opticaldevice of claim 1, wherein the sub-layer comprises a metal oxide, ametal nitride, a metal carbide, a metal oxynitride, or a metaloxycarbide.
 8. The optical device of claim 1, wherein the sub-layercomprises TiO₂.
 9. The optical device of claim 1, wherein the sub-layercomprises a metal oxide selected from the group consisting of aluminumoxide, titanium oxide, TiO₂, tantalum oxide, cerium oxide, zinc oxide,tin oxide, silicon aluminum oxide, tungsten oxide, nickel tungstenoxide, and oxidized indium tin oxide.
 10. The optical device of claim 1,wherein the sub-layer comprises metal nitride selected from the groupconsisting of titanium nitride, aluminum nitride, silicon nitride,tantalum nitride, and tungsten nitride.
 11. The optical device of claim1, wherein the sub-layer comprises a metal carbide selected from thegroup consisting of titanium carbide, aluminum carbide, silicon carbide,tantalum carbide, and tungsten carbide.
 12. The optical device of claim1, wherein the stack is an electrochromic device stack.
 13. The opticaldevice of claim 1, wherein the sub-layer has higher absorptiveproperties relative to the lower conductor layer.
 14. The optical deviceof claim 1, wherein the lower conductor layer comprises SnO₂.
 15. Theoptical device of claim 1, wherein the stack comprises a counterelectrode layer comprising NiWO or NiTaO.